JP5349113B2 - Photosensitive resin composition, dry film and printed wiring board using the same - Google Patents

Abstract

The invention provids a photosensitive resin composition, and a dry film and a printed wiring board using the same, particularly the photosensitive resin composition, its dry film and the printed wiring board made of a cured film such as a solder resist manufatured by them, wherein the cured film such as the solder resist could prevent the ion migration in a fine space circuit. The dry film of the photosensitive resin composition has excellent finger contact drying property, scolder hear resistance, chemical gilding resistance and electrical insulation. The photosensitive resin composition with an alkaline developing property includes an carboxyl-contained resin (B), an photopolymerizable initiator (D), layer-shaped double hydroxides (A) preferably brucite, preferably a compound (C) with alkene unsaturated group; additionally adding a thermal cured component (E), a light cured and thermal cured resin composition is formed.

Description

  The present invention provides a cured product having excellent dryness to touch of a dry coating film, excellent solder heat resistance, electroless gold plating resistance, electrical insulation, etc., and preventing ion migration particularly in a fine pitch circuit. The present invention relates to a photosensitive resin composition capable of forming a cured film. The present invention also relates to a dry film and a cured product using such a photosensitive resin composition, and a printed wiring board having a cured film formed using them.

  Conventionally, alkali-developable photosensitive resin compositions have been used in large quantities as solder resists for printed wiring boards. The solder resist is used for the purpose of protecting the surface layer circuit of the printed wiring board, and requires high solder heat resistance and electrical insulation. In particular, the density of printed wiring boards has been increasing recently, and the circuit has a minimum line size of 10 μm and a space of 10 μm, and higher ion migration resistance is required than ever before. However, since the photosensitive resin used for solder resist is an acrylate compound with fast photoreactivity, it is inferior in hydrophobicity and alkali resistance, easily causes ion migration under high temperature humidification conditions, and causes short circuit between circuits. Was regarded as a problem.

  On the other hand, the thermosetting solder resist includes an epoxy resin having two or more epoxy groups in the molecule, a polyanhydride, and a coupling agent as essential components, and further includes an inorganic ion exchanger, a flame retardant, Furthermore, a composition containing a hydrated metal compound has been proposed (see Patent Document 1). However, when an inorganic ion exchanger is used in an alkali development type solder resist, a large amount of an inorganic component of an alkali developer such as sodium carbonate is absorbed inside the resist, resulting in a worse ion migration resistance. There is.

  Moreover, as an example which used the inorganic layered compound for the alkali-developable type photosensitive resin composition, the epoxy (meth) acrylate compound (B1) having a carboxyl group or the urethane (meth) acrylate compound (B2) having a carboxyl group is used. Compound (B) having an ethylenically unsaturated group including at least one, epoxy resin (E), photopolymerization initiator (D), inorganic layered compound, amine, quaternary ammonium salt, acid anhydride, polyamide A photosensitive resin composition comprising an intercalation compound into which at least one thermal polymerization catalyst selected from the group consisting of a nitrogen-containing heterocyclic compound and an organometallic compound is inserted ( Patent Document 2). This photosensitive resin composition is intended to improve the storage stability of the solder resist by inserting a thermal polymerization catalyst into the inorganic layered compound, but the effect of electrical insulation is not clear. When a thermal polymerization catalyst is inserted into an inorganic layered compound, it is generally considered that the thermosetting reaction of the solder resist is extremely low and effective for storage stability, but conversely, the reaction is difficult to complete. There is a problem that the insulation resistance of the resulting cured coating film becomes low and ion migration is likely to occur.

JP 2006-229127 A (Claims) JP 2003-195486 A (Claims)

The present invention has been made in view of the prior art as described above, and its main purpose is excellent in dryness of touch of a dry coating film, excellent in solder heat resistance, electroless gold plating resistance, electrical insulation and the like. In particular, an object of the present invention is to provide a photosensitive resin composition capable of forming a cured film such as a solder resist that prevents ion migration in a fine pitch circuit.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a photosensitive resin composition, and a cured film such as a solder resist using the dry film and the cured product. It is in providing the printed wiring board formed by.

式中、Ｍ^２＋はＭｇ^２＋，Ｆｅ^２＋，Ｚｎ^２＋，Ｃａ^２＋，Ｌｉ^２＋，Ｎｉ^２＋，Ｃｏ^２＋，Ｃｕ^２＋等の２価の金属陽イオン、Ｍ^３＋はＡｌ^３＋，Ｆｅ^３＋，Ｍｎ^３＋等の３価の金属陽イオン、Ａ^ｎ−はＣＯ_３ ^２−を表し、各元素及び原子団の下付き添字は各元素及び原子団の比率を表し、Ｘは０＜Ｘ≦０．３３、ｍはｍ≧０である。ｍはｍ≧０であるが、脱水により大きく変わる。
（ａ）不飽和カルボン酸と、不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂、
（ｂ）２官能又はそれ以上の多官能固形エポキシ樹脂に（メタ）アクリル酸を反応させ、側鎖に存在する水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂、
（ｃ）２官能固形エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に（メタ）アクリル酸を反応させ、生じた水酸基に２塩基酸無水物を付加させたカルボキシル基含有感光性樹脂、
（ｄ）多官能フェノール化合物に環状エーテル、環状カーボネートを付加させ、得られた水酸基を（メタ）アクリル酸で部分エステル化し、残りの水酸基に多塩基酸無水物を反応させたカルボキシル基含有感光性樹脂、又は
（ｅ）上記の（ａ）〜（ｄ）のいずれか一つの樹脂にさらに分子中に１つのエポキシ基と１つ以上の（メタ）アクリロイル基を有する化合物を付加してなるカルボキシル基含有感光性樹脂。
好ましくは、さらにエチレン性不飽和基を有する化合物（Ｃ）を含有する。好適な態様においては、さらに熱硬化性成分（Ｅ）を含有することにより、光硬化性熱硬化性樹脂組成物とすることができる。別の好適な態様においては、さらに着色剤を含有する。 In order to achieve the above object, according to the present invention, in an alkali-developable photosensitive resin composition containing a carboxyl group-containing resin (B) and a photopolymerization initiator (D), the following general structural formula ( Photosensitivity containing the layered double hydroxide (A) represented by I) and the carboxyl group-containing resin (B) containing one or more of the following (a) to (e): A resin composition is provided.

In the formula, M ²⁺ is a divalent metal cation such as Mg ²⁺ , Fe ²⁺ , Zn ²⁺ , Ca ²⁺ , Li ²⁺ , Ni ²⁺ , Co ²⁺ , Cu ²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Mn ^3+, etc. trivalent metal ^{cation, a n-represents} _CO ^{3 2-,} subscripts of the elements and atomic groups represent the ratio of each element and atomic group, X is 0 <X ≦ 0.33, m Where m ≧ 0. m is m ≧ 0, but varies greatly with dehydration.
(A) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound,
(B) a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional solid epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain;
(C) Carboxy group-containing polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional solid epoxy resin with epichlorohydrin and reacting (meth) acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl group Photosensitive resin,
(D) A carboxyl group-containing photosensitivity obtained by adding a cyclic ether or cyclic carbonate to a polyfunctional phenol compound, partially esterifying the resulting hydroxyl group with (meth) acrylic acid, and reacting the remaining hydroxyl group with a polybasic acid anhydride. Resin, or (e) a carboxyl group obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule to any one of the resins (a) to (d) above Contains photosensitive resin.
Preferably, it further contains a compound (C) having an ethylenically unsaturated group. In a suitable aspect, it can be set as a photocurable thermosetting resin composition by containing a thermosetting component (E) further. In another preferred embodiment, a colorant is further contained.

In particular, in the above general structural formula (I), a hydrotalcite-like compound in which the divalent metal cation M ²⁺ is composed of Mg ²⁺ and the trivalent metal cation M ³⁺ is composed of Al ³⁺ is preferable.
Such a photosensitive resin composition, in particular, a photocurable / thermosetting resin composition containing a thermosetting component (E) can be suitably used for forming a solder resist on a printed wiring board.

  Further, according to the present invention, a dry film obtained by applying and drying the photosensitive resin composition on a film, or further obtained by applying and drying the photosensitive resin composition or this photosensitive resin composition on a carrier film. Provided is a cured product obtained by photocuring or further heat-curing a dry film, especially a cured product obtained by photocuring on copper, or a cured product obtained by photocuring in a pattern or further thermosetting. Is done. Furthermore, according to this invention, the printed wiring board which has the said hardened | cured material is also provided.

The photosensitive resin composition of the present invention is an alkali-developable photosensitive resin composition containing a carboxyl group-containing resin (B) and a photopolymerization initiator (D), and further includes a layered double hydroxide (A), particularly Because it contains hydrotalcite and hydrotalcite-like compound having the structure represented by the general formula (1), it is excellent in dry touch of dry coating, solder heat resistance, electroless gold plating resistance, electricity A cured film excellent in insulation and the like and having high ion migration resistance especially when humidified at high temperature can be formed. Moreover, since the carboxyl group-containing resin (B) is contained together with the layered double hydroxide (A), the resulting photosensitive resin composition can be developed with an alkaline aqueous solution.
Therefore, the photosensitive resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

  As described above, the photosensitive resin composition of the present invention is characterized by the carboxyl group-containing resin (B) (carboxyl group-containing photosensitive resin (B-1), or compound (C) having an ethylenically unsaturated group) In the alkali-developable photosensitive resin composition containing the combined non-photosensitive carboxyl group-containing resin (B-2)) and photopolymerization initiator (D), the layered double hydroxide (A), particularly the above The point is that the compound represented by the general formula (1) is used.

According to the study by the present inventors, the dry coating film of the photosensitive resin composition obtained by containing the layered double hydroxide (A), particularly the compound represented by the general formula (1), is touched. It was found that the generation of ion migration can be suppressed over a long period of time as compared with the case where the dried film is excellent and the cured film does not contain the layered double hydroxide (A) under high temperature humidification conditions. This is considered to be derived from the property that the layered double hydroxide (A) acts as an anion exchanger under acidic conditions. That is, it is generally known that in a copper circuit under a high temperature humidification condition, the application of a voltage makes the anode acidic and the cathode alkaline. Since anions such as chloride ions are attracted to the anode, the layered double hydroxide (A) having an anion exchange action under acidic conditions is very efficiently halogenated ions, particularly the causative substances of ion migration, It can be considered that chlorine ions are incorporated into the structure, and thereby the occurrence of ion migration can be suppressed for a long time. This phenomenon is an efficient effect not seen in other ion exchangers, and the layered double hydroxide (A) has particularly CO ₃ ²⁻ as an anion, sodium carbonate. It is considered that a stable effect was obtained without ion exchange of an anion (for example, CO ₃ ²⁻ ) of the alkali developer even during the development process using the alkali developer such as. These phenomena were unique effects not seen in other ion exchangers.

  In general, when a photosensitive resin composition is applied to a substrate or the like, a layered inorganic compound such as organic bentonite or montmorillonite may be used for the purpose of suppressing sagging. However, these are known to adversely affect electrical properties. On the other hand, the composition in which the layered double hydroxide (A) such as the hydrotalcite compound of the present invention is blended can remarkably improve the electrical properties, improve the thixotropy, and the substrate. A synergistic effect was also obtained in that dripping could be suppressed when the photosensitive resin composition was applied to the film.

Hydrotalcite and hydrotalcite-like compounds are a kind of naturally occurring clay minerals, for example, positively charged basic layer [Mg _1-X Al _X (OH) ₂ ] ^{X +} and negatively charged intermediate layer [(CO ₃ ) _{X / 2} · mH ₂ O] A layered inorganic compound consisting of ^X- . Many divalent and trivalent metals have the same layered structure, and the general structural formula is represented by the formula (I).
These hydrotalcite and hydrotalcite-like compounds have some characteristics not found in other inorganic layered compounds such as montmorillonite, such as anion exchange capacity and thermal decomposition-rehydration reaction. There are few examples.

Specific examples of the layered double hydroxide (A) include Indigirite Mg ₂ Al ₂ [(CO ₃ ) ₄ (OH) ₂ ] .15H ₂ O, Fe ²⁺ ₄ Al ₂ [(OH) ₁₂ CO ₃ ]. 3H ₂ O, Quintinite Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · H ₂ O, Manasseite Mg ₆ Al ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, SjOegrenite Mg ₆ Fe ³⁺ ₂ [(OH) ₁₆ CO _{3] · 4H 2 O, Zaccagnaite} Zn 4 Al 2 (CO 3) (OH) 12 · 3H 2 O, Desautelsite Mg 6 Mn 3+ 2 [(OH) 16 CO 3] · 4H 2 O, hydrotalcite Mg 6 Al 2 [ (OH) ₁₆ CO ₃ ] · 4H ₂ O, Pyroaurite Mg ₆ Fe ^{3 +} ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Reevesite Ni ₆ Fe ³⁺ ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Stichtit e Mg ₆ Cr ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Takovite Ni ₆ Al ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, etc. may be mentioned, and these may be used alone or in combination of two or more. be able to.

Moreover, as a commercial item of synthetic hydrotalcite, Kyowa Chemical Industry Co., Ltd. product; Alkamizer, DHT-4A, Kyoward 500, Kyoward 1000, Sakai Chemical Co., Ltd. STABIACE series HT-1, HT -7, HT-P and the like.
Particularly preferred are synthetic hydrotalcites having an average particle size of 2 μm or less, more preferably 1 μm or less. Further, these hydrotalcites can be used in the anhydrous state as they are in the form of hydrates or after baking.

  The compounding quantity of the said layered double hydroxide (A) is 1-50 mass parts with respect to 100 mass parts of carboxyl group-containing resin (B) mentioned later, Preferably it is 2-50 mass parts, More preferably, it is 5-40. The range of parts by mass is appropriate. If the blended amount of the layered double hydroxide (A) is more than the above range, the viscosity and thixotropy of the composition will be too high, the printability may be lowered, and the cured product may be brittle. Absent. On the other hand, the case of less than 1 part by mass is not preferable because the ion migration resistance effect is impaired.

  The composition containing the layered double hydroxide (A) according to the present invention has an alkali-developable photosensitive resin composition, that is, a carboxyl group-containing photosensitive resin (B-1), or an ethylenically unsaturated group. A composition containing a non-photosensitive carboxyl group-containing resin (B-2) in combination with the compound (C) and a photopolymerization initiator (D), and a thermosetting component (E), for example, described later It is a photocurable thermosetting resin composition containing a thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule.

As the carboxyl group-containing resin (B), various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting alkali developability can be used. In particular, a carboxyl group-containing photosensitive resin (B-1) having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In addition, when using only carboxyl group-containing resin (B-2) which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, two or more ethylenic in the molecule | numerator mentioned later It is necessary to use a compound (C) having an unsaturated group, that is, a photopolymerizable monomer.
As specific examples of the carboxyl group-containing resin (A), compounds listed below (any of oligomers and polymers) can be suitably used.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as

  (8) (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenolic compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polybasic acid. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

  (10) The resin of the above (1) to (9) further has one epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound.

These carboxyl group-containing resins (B) can be used without being limited to those listed above, and can be used by mixing one kind or plural kinds. In this specification, (meth) acrylate is , Acrylate, methacrylate and mixtures thereof, as well as other similar expressions.

  Among the carboxyl group-containing resins (B), the carboxyl group-containing resins (1), (2), (3), (5) and (9) which do not use an epoxy resin as a starting material have very few chlorine ion impurities. However, it became clear that the electrical characteristics were further improved by adding the layered double hydroxide (A) according to the present invention. This is presumably because the layered double hydroxide not only serves as an anion exchanger but also stabilizes the acid component. In addition, a carboxyl group-containing resin using an epoxy resin as a starting material, for example, a carboxyl group-containing photosensitive resin obtained by adding glycidyl (meth) acrylate to the carboxyl group-containing photosensitive resin of (7) ((7) + ( 10)) has a larger amount of chlorine ion impurities than the carboxyl group-containing photosensitive resin (7) used as the starting material. However, when the layered double hydroxide (A) is used in accordance with the present invention, the starting material is used. It was confirmed that the electrical characteristics were dramatically improved as compared with the composition containing the carboxyl group-containing photosensitive resin (7) and the layered double hydroxide (A). This was an unexpected effect. Therefore, a more effective carboxyl group-containing resin (B) is a carboxyl group-containing resin that does not use the epoxy resin described in (1), (2), (3) and (9) as a starting material among the carboxyl group-containing resins. It is a compound obtained by modifying the resin and its modified product according to (5) and (6) and the carboxyl group-containing resins (1) to (9) as described in (10).

Since the carboxyl group-containing resin (B) as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
Moreover, the acid value of the said carboxyl group containing resin (B) is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (B) changes with resin frame | skeleton, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The blending amount of such a carboxyl group-containing resin (B) is appropriately 20 to 80% by mass, preferably 30 to 60% by mass in the entire composition. When the blending amount of the carboxyl group-containing resin (B) is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.

  The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photosensitive resin composition of the present invention is photocured by irradiation with active energy rays, and the carboxyl group-containing resin (B). Is insolubilized in an aqueous alkali solution or assists insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates and the like, can be used alone or in combination of two or more.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the compound (C) which has 2 or more ethylenically unsaturated groups in such a molecule | numerator is 5-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably A ratio of 1 to 70 parts by mass is appropriate. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

式中、Ｒ^１は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^２は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^５及びＲ^６は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ^７及びＲ^８は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^７及びＲ^８の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 As the photopolymerization initiator (D), an oxime ester photopolymerization initiator (D1) having a group represented by the following general formula (II), an α-amino having a group represented by the following general formula (III) One or more photopolymerization initiators selected from the group consisting of an acetophenone photopolymerization initiator (D2) and / or an acylphosphine oxide photopolymerization initiator (D3) having a group represented by the following formula (IV) It is preferable to use an agent.

In the formula, R ¹ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Represents one group, provided that one of R ⁷ and R ⁸ may represent an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

式中、Ｒ^９は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１０、Ｒ^１２は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^１１は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。

In the formula, R ⁹ is a hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl group, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１３、Ｒ^１４及びＲ^１９は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、
Ｍは、Ｏ、Ｓ又はＮＨを表し、
ｍ及びｐは、それぞれ独立に０〜５の整数を表す。

In formula, R <^13> , R <^14> and R < ¹⁹ > represent a C1-C12 alkyl group each independently,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
m and p each independently represents an integer of 0 to 5.

  Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The blending amount of such a photopolymerization initiator (D) is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). Is appropriate. When the blending amount of the photopolymerization initiator (D) is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated. Therefore, it is not preferable. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (D) becomes violent, and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (II), the blending amount thereof is preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin (B). 20 mass parts, More preferably, the range of 0.01-5 mass parts is desirable.

  Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the photosensitive resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. , Xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (B). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B). It is. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

  In the photosensitive resin composition of the present invention, known and commonly used N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole and the like can be blended as a chain transfer agent in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group, such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  In addition, the polyfunctional mercaptan-based compound is not particularly limited. For example, fats such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, etc. Aromatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (Mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetra Poly (mercaptoacetate) s of polyhydric alcohols such as poly (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) s of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, and poly (mercaptobutyrate) such as pentaerythritol tetrakis (3-mertapbutyrate).

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

  In particular, as a heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the photosensitive resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

These photopolymerization initiators, photoinitiator assistants, sensitizers and chain transfer agents can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, sensitizer and chain transfer agent is preferably in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (B). . When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In the photosensitive resin composition of the present invention, a thermosetting component (E) can be used to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds. , Known thermosetting resins such as oxazoline compounds and carbodiimide resins can be used. Particularly preferred is a thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  The thermosetting component (E) having two or more cyclic (thio) ether groups in such a molecule is either a three-, four- or five-membered cyclic ether group or a cyclic thioether group in the molecule. Or a compound having two or more two types of groups, for example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1), at least two oxetanyl in the molecule Examples thereof include a compound having a group, that is, a polyfunctional oxetane compound (E-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (E-3).

  Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphtalene group-containing epoxy such as HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; Cyclohexylmaleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (E-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound (E-3) having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (B). The range which becomes -2.5 equivalent, More preferably, 0.8-2.0 equivalent is suitable. When the blending amount of the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  Moreover, the compound which has a 2 or more isocyanate group or blocked isocyanate group in 1 molecule can be added as a thermosetting component. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two or more in one molecule. And a compound having a blocked isocyanate group, that is, a blocked isocyanate compound.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (B). A ratio of 2 to 70 parts by mass is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

  Furthermore, examples of other thermosetting components include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (manufactured by Sanwa Chemical Co., Ltd.) and the like. The said thermosetting component can be used individually or in combination of 2 or more types.

  When the thermosetting component (E) having two or more cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The compounding amount of these thermosetting catalysts is sufficient in the usual quantitative ratio. For example, the thermosetting component (E) having a carboxyl group-containing resin (B) or two or more cyclic (thio) ether groups in the molecule. Preferably it is 0.1-20 mass parts with respect to 100 mass parts, More preferably, it is 0.5-15.0 mass parts.

  In the photosensitive resin composition of the present invention, an adhesion-imparting agent can be blended in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Specifically, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Accelel M manufactured by Kawaguchi Chemical Industry Co., Ltd.) 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazol-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzo Examples include triazole, amino group-containing benzotriazole, and silane coupling agent.

  The photosensitive resin composition of this invention can mix | blend a coloring agent (F). As the colorant, conventionally known colorants such as red (F-1), blue (F-2), green (F-3), yellow (F-4) can be used, and pigments, dyes, Any of pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant (F-1):
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant (F-2):
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 , Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant (F-3):
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant (F-4):
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending ratio of the colorant (F) as described above is not particularly limited, but is preferably 0 to 10 parts by weight, particularly preferably 0.1 to 100 parts by weight of the carboxyl group-containing resin (B). A proportion of 5 parts by weight is sufficient.

  The photosensitive resin composition of this invention can mix | blend a filler (G) as needed, in order to raise the physical strength etc. of the coating film. As such a filler (G), publicly known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler (G) is preferably 75% by mass or less, more preferably 0.1 to 60% by mass of the total amount of the composition. If the blending amount of the filler exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition is increased, and the coating and moldability are lowered, and the cured product becomes brittle.

Furthermore, the photosensitive resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (B), the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. be able to.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  Generally, in many polymer materials, once oxidation starts, oxidative degradation successively occurs one after another, resulting in a decrease in the function of the polymer material. Therefore, the photosensitive resin composition of the present invention prevents oxidation. Therefore, (1) radical scavenger (H-1) that invalidates the generated radicals and / or (2) the generated peroxide is decomposed into harmless substances to prevent generation of new radicals. An antioxidant (H) such as an oxide decomposing agent (H-2) can be added.

  Specific examples of the antioxidant (H-1) acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t. -Butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-) phenol compounds such as t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis 2,2,6,6-tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant (H-2) acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, di And sulfur compounds such as stearyl 3,3′-thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant (H) can be used individually by 1 type or in combination of 2 or more types.

  In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the photosensitive resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. Ultraviolet absorber (I) can be used.

  Examples of the ultraviolet absorber (I) include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

The ultraviolet absorber (I) may be a commercially available product, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name) and the like.
Said ultraviolet absorber (I) can be used individually by 1 type or in combination of 2 or more types, and is obtained from the photosensitive resin composition of this invention by using together with the said antioxidant (H). The molded product can be stabilized.

  The photosensitive resin composition of the present invention may further comprise, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thixotropic agents such as finely divided silica, organic bentonite, and montmorillonite, silicone-based, fluorine-based, and polymer-based materials. Known additives such as antifoaming agents and / or leveling agents such as silane coupling agents such as imidazole, thiazole and triazole, antioxidants, rust inhibitors and the like can be blended.

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3). The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Furthermore, in the case of the composition containing the thermosetting component (E), for example, by heating and curing at a temperature of about 140 to 180 ° C., the carboxyl group of the carboxyl group-containing resin (B) and molecules Thermosetting component (E) having two or more cyclic ether groups and / or cyclic thioether groups reacts, and has excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. A cured coating film can be formed. In addition, even when the thermosetting component (E) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Depending on the purpose and application, heat treatment (thermosetting) may be performed.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  Volatile drying performed after applying the photosensitive resin composition of the present invention is performed in a dryer using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam). It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.

After applying the photosensitive resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The photosensitive resin composition of the present invention is in the form of a dry film having a solder resist layer formed by previously applying and drying a solder resist on a film of polyethylene terephthalate or the like, in addition to the method of directly applying to the base material in liquid It can also be used. The case where the photosensitive resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable photosensitive resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying an alkali-developable photosensitive resin composition to a carrier film or cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, and the like, and then drying. The
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis Example 1 (Synthesis of carboxyl group-containing resin (B))
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ), TJ5650J, number average molecular weight 800) 360 g (0.45 mol), dimethylolbutanoic acid 81.4 g (0.55 mol), and n-butanol 11.8 g as molecular weight regulator (reaction terminator) (0.16 mol) was added. Next, 200.9 g (1.08 mol) of trimethylhexamethylene diisocyanate was added as an isocyanate compound having no aromatic ring, and the mixture was heated to 60 ° C. with stirring and stopped, and the temperature in the reaction vessel began to decrease. At that time, the mixture was heated again and stirred at 80 ° C., and it was confirmed that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) disappeared in the infrared absorption spectrum, and the reaction was terminated. Subsequently, carbitol acetate was added so that a solid content might be 60 wt%, and the viscous liquid carboxyl group-containing polyurethane containing a diluent was obtained. This is referred to as B-1 varnish. This corresponds to the carboxyl group-containing urethane resin (2) described above for the carboxyl group-containing resin (B).

Synthesis Example 2 (Synthesis of carboxyl group-containing resin (B))
2400 g of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (TJ5650J, number average molecular weight 800, manufactured by Asahi Kasei Chemicals Corporation) in a reaction vessel equipped with a stirrer, a thermometer and a condenser. (3 mol), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound were added. Next, 1887 g (8.5 mol) of isophorone diisocyanate was added as a polyisocyanate, and the mixture was stopped by heating to 60 ° C. while stirring. When the temperature in the reaction vessel began to decrease, the mixture was heated again and stirred at 80 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) had disappeared in the infrared absorption spectrum. Carbitol acetate was added so that the solid content was 50% by mass. This is referred to as B-2 varnish. This corresponds to the terminal (meth) acrylated carboxyl group-containing urethane resin of (5) described above for the carboxyl group-containing resin (B).

Synthesis Example 3 (Synthesis of carboxyl group-containing resin (B))
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 g of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. This is referred to as Resin Solution B-3 Varnish. This corresponds to the carboxyl group-containing photosensitive resin (9) described above for the carboxyl group-containing resin (B).

  The various components shown in Table 1 were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

Performance evaluation:
<Sagging>
The photocurable / thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was polished by buffing, washed with water and dried. The degree of sag when standing vertically for 60 minutes was evaluated.
○: Sagging is not allowed.
Δ: Slight sagging is confirmed.
X: It is confirmed whether it is dripping.

<Optimum exposure amount>
The photocurable / thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate with a copper thickness of 35 μm was buffed, washed with water and dried. It was dried for 60 minutes in a hot air circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when it was performed in seconds was 7 steps, the optimum exposure amount was set.

<Dry touch dryness>
The photocurable / thermosetting resin composition shown in Table 1 was applied on the entire surface of a patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and allowed to cool to room temperature. did. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated.
(Double-circle): When peeling a film, there is no resistance and a mark is not left in a coating film.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

<Resolution>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was applied to the photocurable / thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). As the exposure pattern, a glass dry plate for drawing a 20/30/40/50/60/70/80/90/100 μm line in the space portion was used. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. to draw a pattern, and a cured coating film was obtained by heat curing at 150 ° C. for 60 minutes.
It calculated | required using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times (resolution).

Characteristic test:
The composition of each of the above Examples and Comparative Examples was applied on the entire surface of a patterned copper foil substrate so that the film thickness after drying by screen printing was 20 μm, dried at 80 ° C. for 30 minutes, and then released to room temperature. Cool down. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<Electrical characteristics 1 (insulation reliability, electrode corrosion)>
An evaluation substrate was produced under the above conditions using a comb-type electrode pattern of line / space = 50/50 μm, and electrical characteristics (insulation reliability, electrode corrosivity) were evaluated.
The evaluation method was that this comb-shaped electrode was 121 ° C., 97% R.D. H. A bias voltage of DC 30 V was applied under the heating and humidifying conditions, and the time until insulation deterioration was measured. Here, when the electric resistance value fell below 1 × 10 ⁻⁶ Ω, it was determined that the insulation was deteriorated.
Further, the degree of electrode corrosion (degree of dendrite generation) after 100 hours under the above conditions was evaluated according to the following criteria.
A: Dentite is not generated and discoloration is slight.
○: No dendrite is generated but discoloration is confirmed.
Δ: Dendrite is slightly confirmed.
X: The dendrite grows large between the anode and the cathode.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at 50 ° C. for 30 minutes, and soaking and dissolution of the coating film were confirmed. Further, peeling by tape beer was confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Dry film production>
After appropriately diluting each of the photosensitive resin compositions for solder resist of Example 1 and Comparative Example 1 with methyl ethyl ketone, using an applicator, a PET film (FB manufactured by Toray Industries, Inc.) so that the film thickness after drying becomes 20 μm. −50: 16 μm) and dried at 80 ° C. for 30 minutes to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.): 0.8 MPa, 70 ° C., 1 minute The substrate was heated and laminated under the condition of a degree of vacuum of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.
The evaluation results are shown in Table 2.

Examples 5 to 10, Reference Examples 1 to 3 and Comparative Examples 7 to 15
The various components shown in Table 3 were blended in the proportions (parts by mass) shown in Table 3, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

<Electrical characteristics 2 (insulation reliability, electrode corrosion)>
Each of the compositions of Examples 5 to 10, Reference Examples 1 to 3 and Comparative Examples 7 to 15 has a film thickness after drying by screen printing on a comb-type electrode pattern substrate of line / space = 30/30 μm to 20 μm. The whole surface was coated as such, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The obtained comb-shaped electrode pattern substrate was evaluated for electrical characteristics (insulation reliability, electrode corrosivity).

The evaluation method is that the comb-shaped electrode pattern is 121 ° C., 97% R.D. H. A bias voltage of DC 30 V was applied under the heating and humidifying conditions, and the time until insulation deterioration was measured. Here, when the electric resistance value fell below 1 × 10 ⁻⁶ Ω, it was determined that the insulation was deteriorated.
Further, the degree of electrode corrosion (degree of dendrite generation) after 100 hours under the above conditions was evaluated according to the following criteria.
○: No dendrite is generated.
Δ: Dendrite is slightly confirmed.
X: The dendrite grows large between the anode and the cathode.
The evaluation results are shown in Table 4.

  As shown in Tables 2 and 4, in the case of Examples 1 to 10 and Reference Examples 1 to 3 of the present invention, ion migration may occur while maintaining various physical properties as compared with Comparative Examples 1 to 15. In addition, it was confirmed that the resin composition was extremely excellent in electrical characteristics, particularly electrode corrosivity, and useful as an alkali-developable photosensitive resin composition.

Claims (8)

In the alkali-developable photosensitive resin composition containing the carboxyl group-containing resin (B) and the photopolymerization initiator (D),
Furthermore , it contains a layered double hydroxide (A) represented by the following general structural formula (I) , and
The said carboxyl group containing resin (B) is a photosensitive resin composition characterized by including one type or multiple types of following (a)-(e) .

^{(Wherein, M 2+} is a divalent metal ^{cation, M 3+} is a trivalent metal ^{cation, A n-represents} _CO ^{3 2-,} subscripts of the elements and atomic groups each elements and atomic groups X represents 0 <X ≦ 0.33 and m ≧ 0.)
(A) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound,
(B) a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional solid epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain;
(C) Carboxy group-containing polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional solid epoxy resin with epichlorohydrin and reacting (meth) acrylic acid, and adding a dibasic acid anhydride to the resulting hydroxyl group Photosensitive resin,
(D) A carboxyl group-containing photosensitivity obtained by adding a cyclic ether or cyclic carbonate to a polyfunctional phenol compound, partially esterifying the resulting hydroxyl group with (meth) acrylic acid, and reacting the remaining hydroxyl group with a polybasic acid anhydride. Resin, or
(E) A carboxyl group-containing photosensitivity obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule to any one of the resins (a) to (d) above. resin.   The photosensitive resin composition according to claim 1, further comprising a compound (C) having an ethylenically unsaturated group.   Furthermore, the thermosetting component (E) is contained, The photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. In the general formula (I), 2-valent metal cation ^{M 2+} is ^{Mg 2+,} 3-valent any one of claims 1 to 3 metal cation ^{M 3+} is characterized in that it is a A ^{l 3+} The photosensitive resin composition as described in 2. It is an object for solder resist formation, The photosensitive resin composition as described in any one of Claims 1 thru | or 4 characterized by the above-mentioned. The dry film formed by apply | coating and drying the photosensitive resin composition as described in any one of Claims 1 thru | or 5 on a film. A cured product obtained by photocuring or further thermally curing a photosensitive resin composition according to any one of claims 1 to 5 or a dry film obtained by applying and drying the photosensitive resin composition on a carrier film. . A printed wiring board having the cured product according to claim 7 .